Cure accelerators

ABSTRACT

An epoxy resin composition comprising an epoxy resin component combined with a sufficient amount of an imidazole curative to provide curing of the epoxy resin composition. The epoxy resin composition further includes a non-hydroxyl containing cure accelerator for the imidazole curative.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to cure accelerators suitable for use inaccelerating the cure of epoxy resins, in particular, to theacceleration of the imidazole cure of epoxy resins.

2. Description of Related Art

Epoxy resins are widely used as matrices for fiber-reinforced compositematerials. These assemblies are widely used as structural components, inindustrial and leisure applications, in aerospace and for transportationapplications. Epoxy resins are also used in encapsulation formulationsfor the isolation and immobilization of electronic components as well asin structural adhesives.

There are a number of well-known reaction mechanisms which can be usedto cure epoxy resins. One such mechanism involves the use of an agentwhich behaves as an initiator for the ring opening polymerization of theepoxy ring. Ring opening polymerization can be initiated by a number ofcompounds, common examples of which include tertiary amines andimidazoles.

Imidazoles offer significant benefits when used as epoxy resincuratives. The correct choice of imidazole enables the cure conditionsto be manipulated, which can give benefits in outlife, reactionenthalpy, reaction rate, cure temperature, cost, mechanical performanceand formulation viscosity etc.

For some applications it is important to have an epoxy resin systemwhich cures rapidly at relatively low temperatures, for example 60-80°C., but that will maintain the properties referred to above. Themajority of currently available imidazole-cured epoxy resin formulationsfail to cure within practically useful timescales at low temperatures.Where it is possible to meet the required cure times using existingimidazole/epoxy chemistry, there are often times where a more rapidinitiation of the cure reaction is of benefit. Preferably, this will bemanifested as a faster gel time resulting in quicker structuralimmobilisation of the resin or assembly.

For some applications it is important to have an epoxy resin systemwhich cures rapidly at relatively low temperatures, for example 60-80°C., but that will maintain the properties referred to above. Themajority of currently available imidazole-cured epoxy resin formulationsfail to cure within practically useful timescales at low temperatures.Where it is possible to meet the required cure times using existingimidazole/epoxy chemistry, there are often times where a more rapidinitiation of the cure reaction is of benefit. Preferably, this will bemanifested as a faster gel time resulting in quicker structuralimmobilisation of the resin or assembly.

Until recently, there have been no compounds available that can act asaccelerators for the imidazole-epoxy reaction.

WO 02/081540 discloses the use of alcohols as imidazole cureaccelerators in Resin Transfer Moulding (RTM) systems. However, alcoholsare volatile and so their use as accelerators is unsuitable for manyapplications, particularly those applications where the alcohol has theopportunity to evaporate prior to or during cure.

Therefore, it is an object of the present invention to provide imidazolecure accelerators for epoxy resins which facilitate rapid lowtemperature cure of the resin.

SUMMARY OF THE INVENTION

According to the first aspect of the present invention there is providedan epoxy resin composition comprising at least one epoxy resincomponent, at least one imidazole curative and at least one non-hydroxylcontaining cure accelerator for imidazoles.

Advantageously, compositions of the present invention can be used forsystems where the ultimate glass transition temperature of theformulation is not commensurate with the cure temperature, i.e. theformulation is capable of higher glass transition temperatures than thecure temperature is able to confer on the system, the thermo-mechanicalperformance of the material appears to be enhanced for inclusion ofthese accelerators. This is evidenced by reference to dynamic mechanicalthermal analysis (DMTA) results of cured resin plaques or laminates thatshow an improved modulus hold up from ambient temperature to the E′extrapolated onset Tg, and less evidence of viscous damping attemperatures exceeding the peak tan δ of the formulation. Theimprovement noted is related to the amount of accelerator used in theformulation and the nature of the formulation in which it features.

It has been found that the inclusion of a cure accelerator leads tocompositions having a reduced gel time relative to compositions whichlack a cure accelerator. This offers clear advantages in the way inwhich the composition of the present invention can be processed.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a graph showing the degree of conversion of formulationscontaining cure accelerators over time expressed as a percentage oftotal enthalpy.

DETAILED DESCRIPTION OF THE INVENTION

As referred to herein, gelation/gel time is taken to be the time atwhich the uncured resin composition is no longer fluid and pulls awayfrom the sides of the containing vessel.

Liquid and/or solid type epoxy resins may be used with the presentinvention. These materials have an oxirane ring that can be polymerizedby ring opening and include both monomeric and polymeric types.Furthermore, they may also carry additional substituent functionality.The epoxy resin component may comprise at least one liquid and/or atleast one solid type epoxy resin.

Suitable epoxy resins, which can be used alone or combination, includeany of the following; aromatic glycidyl ethers, aliphatic glycidylethers, glycidyl amines and glycidyl esters.

Suitable aromatic glycidyl ethers, which may be used alone or incombination, include any of the following: diglycidyl ethers ofbisphenol A, bisphenol F and bisphenol S; the glycidyl ethers of thenovolaks obtainable from phenol, cresol, bisphenol A, halogenatedphenols; the diglycidyl ether of tetrabromo bisphenol A, the diglycidylether of tetrabromo bisphenol S; diglycidyl ethers of resorcinol andalkylated resorcinols, the diglycidyl ether of hydroquinone, diglycidylether of 2,5-di-tertiary butyl hydroquinone, the tetraglycidyl ether of1,1-methylenebis(2,7-dihydroxynaphthalene), the diglycidyl ether of4,4′-dihydroxy-3,3′,5,5′-tetramethylbiphenyl, the diglycidyl ether of1,6-dihydroxynaphthalene, the diglycidyl ether of9,9′-bis(4-hydroxyphenyl)fluorene, the diglycidyl ether of the reactionproduct of glycidol and butylated catechol, the triglycidyl ether oftris(p-hydroxyphenyl)methane, the tetraglycidyl ether oftetrakis(p-hydroxyphenyl)ethane.

Suitable aliphatic glycidyl ethers, which may be used alone or incombination include any of the following; diepoxypropane, diepoxybutane,diepoxyhexane, diepoxyoctane, the diglycidyl ether of neopentyl glycol,the diglycidyl ether of cyclohexane dimethanol, the triglycidyl ether ofglycerol, the triglycidyl ether of trimethylolethane, the triglycidylether of trimethylolpropane, the tetraglycidylether of pentaerythritol,3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, bis(2,3-epoxycyclopentyl)ether,dicyclopentanediepoxide, the diglycidyl ether of hydrogenated bisphenolA, bis(3,4-epoxycyclohexylmethyl) adipate.

Suitable glycidyl amines, which may be used alone or in combination,include any of the following: diglycidylaniline, diglycidyl o-toluidine,the tetraglycidyl derivative of diaminodiphenylmethane, tetraglycidylderivative of 3,3′-diethyl-4,4′-diaminodiphenylmethane, thetetraglycidyl derivative of m-xylylenediamine;1,3-bis(diglycidylaminomethyl)cyclohexane; triglycidyl-m-aminophenol andtriglycidyl-p-aminophenol.

Suitable glycidyl esters, which may be used alone or in combination,include any of the following; the diglycidyl ester of phthalic acid, thediglycidylester of 1,2-cyclohexanedicarboxylic acid, the diglycidylester of terephthalic acid, and the diglycidylester of hexahydrophthalicacid.

Taking into account the imidazole curative, the cure accelerator andother additional ingredients as referred to herein the epoxy resin ispreferably present in the composition in an amount up to 100%.Therefore, the epoxy resin typically constitutes from about 50% to about99% by weight of the composition.

Any imidazole derived curative may be used with the present invention.Examples of particularly preferred imidazole curatives are disclosed inEP 0906927 B1.

Particularly suitable imidazole curatives, which may be used alone or incombination include any of the following; imidazole, 2-methylimidazole,2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole,2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole,2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole,1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole,1-aminoethyl-2-methylimidazole, and the like. The imidazole curativepreferably constitutes from about 0.1% to about 30% by weight of theepoxy resin composition.

The use of latent imidazoles offers an additional advantage in that theyprovide some degree of room temperature out-life. As referred to hereinroom temperature means from about 20° C. to about 30° C.

Imidazole cure accelerators suitable for use with the present inventioninclude sulfonamides, benzamides and/or aromatic acid hydrazides. Theexact mechanism by which these materials accelerate imidazole cure isnot clear, although it is believed that they may facilitate epoxy cureby modification of the solubility characteristics of the resinformulation, or by stabilization of some reactive intermediate formedduring the curing mechanism.

Particularly suitable sulfonamides, which may be used alone or incombination include any of the following: N-methyl toluenesulfonamide,N-ethyl toluenesulfonamide, methanesulfonamide, benzenesulfonamide,N-butylbenzenesulfonamide, p-chlorobenzenesulfonamide,o-toluenesulfonamide, p-toluenesulfonamide, andbis(hydroxyethyl)toluenesulfonamide. Monofunctional sulfonamides, suchas those listed here, are preferred. Difunctional (disulfonamides) arenot preferred.

Particularly suitable benzamides, which may be used alone or incombination, include any of the following: n-methyl benzamide andn-methyl toluamide.

Particularly suitable aromatic acid hydrazides, which may be used aloneor in combination include any of the following: benzoic hydrazide,p-toluic hydrazide, m-toluic hydrazide, m-anisic hydrazide,2-chlorobenzoic hydrazide, 2-nitrobenzoic hydrazide, 2-furoic hydrazideand 1-naphthoic hydrazide. Monofunctional aromatic acid hydrazides, suchas those listed here, are preferred. Difunctional aromatic acidhydrazides (dihydrazides) are not preferred.

The imidazole cure accelerator preferably constitutes from about 1% toabout 20% by weight of the epoxy resin composition, more preferably fromabout 5% to about 15% and most preferably from about 7% to about 13%.The relative amounts of imidazole curative and imidazole cureaccelerator in the epoxy resin composition are chosen such that theimidazole functions as the curative agent and the cure acceleratorfunctions as an accelerator for the imidazole curing process.

The epoxy resin composition of the present invention may additionallycomprise performance enhancement or modification agents which may beused alone or in combination. These include, but are not limited to,inorganic fillers such as silica, alumina; additional accelerators;thermoplastics and core shell rubbers; flame retardants which may beintumescents; wetting agents; pigments/dyes; UV absorbers; tougheningparticles; and viscosity modifiers.

According to a second aspect of the present invention there is provideda process for the manufacture of an epoxy resin composition comprisingthe steps of: preparing a mixture comprising an imidazole curative andat least one epoxy resin component, adding a non-hydroxyl containingimidazole cure accelerator to the mixture and curing the system by theapplication of heat.

Preferably, the curing of the system will also include the applicationof pressure. Advantageously, the present invention gives rise to afaster gelling and faster curing system upon the application of heat tothe formulation. This modification allows lower cure temperatures to beconsidered.

Advantageously, the system of the present invention may be cured using acure cycle of 2 hours at 80° C. It is worth noting that representativecure cycles for typical imidazole containing matrices wherein no cureaccelerator is present are 12 to 16 hours at 65° C. and 4 hours at 80°C. Clearly, the system of the present invention offers a more efficientprocess.

It is envisaged that the epoxy resin system of the present inventionwill find utility in one or multi-component systems for Resin TransferMoulding (RTM), Vacuum-assisted Resin Transfer Moulding (VaRTM), LiquidResin Infusion (LRI) and the like. In a still further alternative theresin composition may be such that it has adhesive properties. Suchadhesives may be in the form of a film, a paste, a powder or a liquid.When in the form of a paste, the adhesives can be deliveredconventionally or using cartridge delivery. The epoxy resin system maybe used for component encapsulation and as the matrix resin in fiberreinforced resin assemblies including prepregs, which are used informing such assemblies. When making a prepreg, the matrix resincomposition may be applied to the fibrous web in such a way as to eitherfully or partially impregnate the fibers. Alternatively, the resincomposition may be in a form of a separate layer that is in contact withthe fibers but does not impregnate the fibers until the prepreg iscured. These are by way of examples and do not limit the application ofthis invention.

Thus, according to a further aspect of the present invention there isprovided an epoxy resin adhesive comprising at least one epoxy resincomponent together with at least one imidazole curative and at least onenon-hydroxy containing cure accelerator for imidazoles. Sulfonamides,benzamides and aromatic acid hydrazides are examples of suitablenon-hydroxy containing cure accelerators. Other known imidazolecuratives may be used in accordance with the present invention providedthat they do not contain a hydroxy group.

When in the form of an adhesive, the resin composition may be in theform of a thin film. Alternatively, the composition may be in the formof a one or two component paste, which may be delivered in a number ofways including from a pot, from a mechanized, powered delivery pump, andvia a cartridge system. The epoxy resin, imidazole curative andimidazole cure accelerator of the resin composition are as hereinbeforedescribed.

The invention will now be described by way of example only withreference to the following examples. All the mixing was done by hand atroom temperature and continued until a homogeneous mix was obtained.

Example 1

1.0 g of 1-(1-imidazolyl)-2-hydroxyoctadecane, Curative I, a latentimidazole curative which is the subject of EP 0906927 B1 was added to8.0 g of Epikote 828 a diglycidyl ether of bisphenol-A supplied byResolution Resins, Rotterdam, Holland, 1.0 g of a specified imidazolecuring accelerator was added to the mixture to provide a test sample.All of the accelerators were obtained from Aldrich Chemical Company,Gillingham, UK. Each test sample was subjected to gel time experimentsthat were performed at 80° C. in a thermostated oil bath on 10 g of thetest sample referred to above. The gel time was determined manually tobe the time when the liquid test sample became elastic.

A control sample (the chosen imidazole plus resin, with no addedaccelerator) was run along with each set of test samples. The gel timeswere normalised within each set by dividing the accelerated gel time bythe control gel time.

A second series of gel experiments were conducted whereby Curative I wassubstituted by 0.50 g 2-phenylimidazole (Aldrich Chemical Company,Gillingham, UK), and 0.94 g of the imidazole cure accelerator wereadded. The results of both experiments are shown in Table 1 below. Theconcentration for each imidazole in the control, i.e. withoutaccelerator, was selected so as to result in a gel time for the controlsystem of 25 to 30 minutes.

TABLE 1 Gel time relative to control Cure Accelerator Curative I2-phenyl imidazole None (Control) 1 1 N-methyl toluenesulfonamide 0.560.79 Methanesulfonamide 0.61 N-ethyl toluenesulfonamide 0.67 0.88N-Butylbenzenesulfonamide 0.67 Benzenesulfonamide 0.65 1.08p-chlorobenzenesulfonamide 0.54 0.96 o-toluenesulfonamide 0.69p-toluenesulfonamide 0.58 0.92 Bis(hydroxyethyl)toluenesulfonamide 0.81Naphthosultam 0.89 Ethylenebisstearamide 1.04 Valerolactam 1 Laurolactam0.96

Table 1 shows that most of the sulfonamides tested gave some degree ofcure acceleration. However, as can be observed from the last 3 examplesin the table, simple amides did not accelerate the cure of the resin.

Example 2

1.0 g of Curative I was added to 8.0 g of Epikote 828. 1.0 g of aspecified imidazole cure accelerator was added to the mixture to providetest samples.

The test samples were subjected to the gel experiments described above.The results are shown in table 2.

TABLE 2 Cure Accelerator Gel Time Relative to Control Benzoic hydrazide0.38 p-Toluic hydrazide 0.42 m-Toluic hydrazide 0.40 m-Anisic hydrazide0.40 2-Chlorobenzoic hydrazide 0.41 2-Nitrobenzoic hydrazide 0.392-Furoic hydrazide 0.39 1-Naphthoic hydrazide 0.45 N-Methylbenzamide0.83 N-Methyltoluamide 0.82

It can be seen that lower molar mass hydrazides have a more markedeffect upon the acceleration of the cure than either the benzamides orthe sulfonamides.

Example 3

Differential Scanning Calorimetry (DSC) studies were carried out toexamine the rate of conversion of formulations containing cureaccelerators. By way of example, the following formulations weresubjected to both dynamic and isothermal DSC studies. LY1556 is an epoxyresin available from Huntsman Advanced Materials, Duxford, England

TABLE 3 Additive Formulation A Formulation B LY1556 8.43 g 9.7 g2-phenylimidazole 0.30 g 0.3 g N-ethyltoluenesulfonamide (ETS) 1.27 g —

A Mettler Toledo Differential Scanning Calorimeter (DSC), model DSC822E,was used to measure the total reaction enthalpy from each of theformulations. The evaluations were carried out in dynamic mode from −35°C. to +250° C. at 20° C. per minute heat up rate. Formulation A wasfound to have a total reaction enthalpy of 360 J/g, whilst formulation Bwas found to have a reaction enthalpy of 310 J/g despite having 15% moreresin present. While not wishing to be bound by this theory, this couldindicate that perhaps the accelerator is facilitating a greater degreeof reaction. Taking these enthalpy data as a measure of total possiblereaction, isothermal DSC runs were carried out at a typical curetemperature of 80° C.

Example 4

By way of another example and to further illustrate the efficacy of theaccelerator, dynamic DSC analyses were conducted on the formulationsshown in Table 4.

TABLE 4 Formulation Formulation Formulation Formulation Additive C D E FLY1556 9.0 g 7.73 g 8.73 g — Curative I 1.0 g 1.0 g — 5.0 g ETS — 1.27 g1.27 g 5.0 g

Formulations E and F showed no evidence of any reaction (no endothermicor exothermic changes attributable to chemical reaction). This showsthat (a) the accelerator does not have the potential to cure the epoxyresin alone under these conditions and that (b) there is no discerniblereaction of Curative I with the accelerator. Formulation F does show anendotherm attributable to a melting event (comprising melting of boththe curative and accelerator). Formulation E does not show anydiscernible melting event as the accelerator is totally in solution inthe resin.

The dynamic DSC analysis of Formulation C shows a melting endothermcorresponding to fusion of Curative I followed by a curing exotherm. Theonset of this exotherm is at 120° C. and it peaks at 146° C. The totalenergy release is of the order of about 400 J/g and the reaction profiledoes not appear to be complete before 210° C. The DSC reports a similarmelting transition for Formulation D. The onset of reaction is some 20°C. lower than formulation A and the reaction profile is of a differentshape. The main peak of this exotherm appears at 137° C., and the totalenergy release this time is of the order of 450 J/g, despite there beinga lower epoxy content for reaction in this mixture. The reaction profileis narrower than formulation C, with all measurable cure being completeby 190° C. on this dynamic analysis.

The invention will now be described further by way of example only withreference to FIG. 1, which is a graph showing the degree of conversionof formulations containing cure accelerators over time expressed as apercentage of total enthalpy.

FIG. 1 shows that the reaction proceeds markedly faster with theaccelerator present than without, reaching 95% conversion in less thanhalf the time it takes for the non-accelerated sample to reach thispoint. The increased reaction rate is evident from the outset of theexperiment, but is also evident in the latter stages of reaction (>60%conversion) where rate continues to be high instead of tailing off as inthe non-accelerated formulation.

It is of course to be understood that the above-described examples areby way of illustration only. Many modifications and variations arepossible.

1. A process for the manufacture of a cured epoxy resin compositioncomprising the steps of: a) preparing a mixture comprising an epoxyresin component combined with a sufficient amount of an imidazolecurative to provide curing of said epoxy resin composition, said epoxyresin composition further comprising a cure accelerator for saidimidazole curative, said cure accelerator comprising an aromaticmonofunctional acid hydrazide, wherein the weight ratio of saidimidazole curative to said cure accelerator is about 1:1; and b) curingsaid mixture with said imidazole curative.
 2. A process for themanufacture of a cured epoxy resin composition according to claim 1wherein the resin component is selected from the group consisting ofaromatic glycidyl ethers, aliphatic glycidyl ethers, glycidyl amines,glycidyl esters and combinations thereof.
 3. A process for themanufacture of a cured epoxy resin composition according to claim 1wherein said imidazole curative is selected from the group consisting ofimidazole, 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole,2-heptadecylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole,2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole,1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole,1-cyanoethyl-2-methylimidazole, 1-aminoethyl-2-methylimidazole andcombinations thereof.
 4. A process for the manufacture of a cured epoxyresin composition according to claim 1 wherein said aromaticmonofunctional acid hydrazide is selected from the group consisting ofbenzoic hydrazide, p-toluic hydrazide, m-toluic hydrazide, m-anisichydrazide, 2-chlorobenzoic hydrazide, 2-nitrobenzoic hydrazide, 2-furoichydrazide, 1-naphthoic hydrazide and combinations thereof.
 5. A methodfor bonding two objects together, said method comprising the steps of:a) applying an epoxy resin composition to one or both of said objects,said epoxy resin composition comprising a mixture comprising an epoxyresin component combined with a sufficient amount of an imidazolecurative to provide curing of said epoxy resin composition, said epoxyresin composition further comprising a cure accelerator for saidimidazole curative, said cure accelerator comprising an aromaticmonofunctional acid hydrazide, wherein the weight ratio of saidimidazole curative to said cure accelerator is about 1:1; and b) bondingsaid objects together by curing said epoxy resin composition with saidimidazole curative.
 6. A method according to claim 5 wherein the resincomponent is selected from the group consisting of aromatic glycidylethers, aliphatic glycidyl ethers, glycidyl amines, glycidyl esters andcombinations thereof.
 7. A method according to claim 5 wherein saidimidazole curative is selected from the group consisting of imidazole,2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole,2-heptadecylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole,2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole,1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole,1-cyanoethyl-2-methylimidazole, 1-aminoethyl-2-methylimidazole andcombinations thereof.
 8. A method according to claim 5 wherein saidaromatic monofunctional acid hydrazide is selected from the groupconsisting of benzoic hydrazide, p-toluic hydrazide, m-toluic hydrazide,m-anisic hydrazide, 2-chlorobenzoic hydrazide, 2-nitrobenzoic hydrazide,2-furoic hydrazide, 1-naphthoic hydrazide and combinations thereof. 9.In a process for curing an epoxy resin with an imidazole curative,wherein the improvement comprises accelerating the imidazole curing ofsaid epoxy resin by adding a sufficient amount of a cure accelerator tosaid epoxy resin so that the weight ratio of said imidazole curative tosaid cure accelerator is about 1:1, said cure accelerator comprising anaromatic monofunctional acid hydrazide.
 10. An improved processaccording to claim 9 wherein the epoxy resin is selected from the groupconsisting of aromatic glycidyl ethers, aliphatic glycidyl ethers,glycidyl amines, glycidyl esters and combinations thereof.
 11. Animproved process according to claim 9 wherein said imidazole curative isselected from the group consisting of imidazole, 2-methylimidazole,2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole,2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole,2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole,1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole,1-aminoethyl-2-methylimidazole and combinations thereof.
 12. An improvedprocess according to claim 9 wherein said aromatic monofunctional acidhydrazide is selected from the group consisting of benzoic hydrazide,p-toluic hydrazide, m-toluic hydrazide, m-anisic hydrazide,2-chlorobenzoic hydrazide, 2-nitrobenzoic hydrazide, 2-furoic hydrazide,1-naphthoic hydrazide and combinations thereof.